Deacetylated chitin shrinkproofing of wool and product



. of the prior art methods. materials used for treatment of the wool were fibers themselves.

Patented Feb. 16, 1954 UNITED STATS PATENT OEHQE DEACETYLATED CHITIN SHRINKPROOFING F WOOL AND PRODUCT Jersey a corporation of New No Drawing. Application November 5, 1949, Serial No. 125,837

18 Claims.

This invention relates to the shrinkproofing of wool with chitin derivatives and more particularly by the utilization of substantially undegraded, at least partially deacetylated chit n, to the shrinkproofed products themselves, to intermediates for producing such shrinkproofed products, and to methods and baths for producing such shrinkproofed and intermediate products.

A Wide variety of methods have been suggested from time to time in the prior art for the shrinkproofing of wool. The use of older methods like the so called chlorination process was not satisfactory because it involved damage to or affected fibers physically militating against their resistance to wear, etc. More recent methods have included the use of various types of polymers and copolymers for application to the wool but these have all been subject to some type of disadvantage or another. This is true generally to the utilization of butadiene polymers and copolymers and also to the use of the melamine shrinkproofing processes. Disadvantages in the prior art methods arose from a number of different factors some affecting one, while others afiect another In some instances the not themselves stable. In other cases there was serious efiect physically or chemically on the In other cases the methods necessary for producing shrinkproofing effects were not commercially feasible. In other cases the materials applied for shrinkproonng were not sufiiciently fast during washing or other laundering operations. In other instances, a great deal of deposited material had to be employed which interfered substantially with the hand of the Wool.

Among the objects of the present invention is the production of shrinkproofed wool free from the difficulties and disadvantages of the prior art processes and products, by utilization of chitin derivatives for these purposes.

Other objects include the production of shrinkprooied wool which is flexible and resistant to abrasion when the treated wool is hand worked.

Objects of the invention include both the products as Well as the methods of producing such products.

Still further objects and advantages of the present invention will appear from the more detailed description set forth below, it being understood that such more detailed description is given by way of illustration and explanation only, and not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

In accordance with the present invention, shrinkproofed wool of substantially normal hand is produced by utilizing as the shrinkproofing deposit on the wool or in fibers thereof to prevent fiber travel, of substantially undegraded at least partially deacetylated chitin. Such material is available as a commercial product in recent years and may be produced in highly purified form as a substantially pure white at least partially deacetylated chitin of very desirable characteristics for utilization in the shrinkproofing of wool.

Chitin itself may be referred to as a polymeric acet'amino carbohydrate derivative which occurs in nature in various forms and particularly in the crustacea such as crabs, lobsters, shrimp, etc., from the horny exo-skeletons of which it may be readily obtained; other sources including the order of insecta such as grasshoppers, and beetles, etc. Chitin may be referred to as comparable in these structures to cellulose as a structural unit in other connections, the building stone of chitin being acetylated chitosamine as against the glucose structural unit of cellulose. The at least partially deacetylated chitin may be readily produced by methods heretofore available in the art and need not be specifically elaborated on at this point. Some of the properties of the deacetylated chitin however may be referred to in this connection. It is available in various grades for utilization for present purposes depending on the methods which have been used in its isolation and purification. All of the products however are properly classified as non-degraded, that is nondepolymerized, at least partially deacetylated chitin. The term non-degraded or undegraded is used in the same sense in which it is used in cellulose chemistry to refer to a material which has not been broken down so that it will not give or deposit a continuous film from solution. The at least partially deacetylated chitin which is used in accordance with this invention is therefore substantially non-degraded.

It exists as stated in a variety of forms de- 3. pending on the extent of the nitrogen as free amino groups and also on various conditions which markedly effect its viscosity, etc., during its production or purification or subsequent handling. As a general rule all of the acetyl groups are not removed from chitin although a large part of them are removed. In general from 80 to 90% of nitrogen appears as free amino groups with the proportions of '70 to 90% preferred in the material particularly useful in accordance with the present invention. The viscosity of the at least partially deacetylated chitin which is used, may vary quite substantially as for example from about 1 to 1000 centi'poises with a preferred range in the order of. -5 to -:centipoises. The viscosity may be stated to be measured desirably on a 0.25% solution of the deacetylated chitin in 0.25% aqueous acetic acid at C. The viscosity as indicated is a variant which may be controlled as desired particularly in the materials which contain 70% to 90% of the nitrogen in the form of free amino groups.-

The chitin most desirably employed for present purposes is one whose relative viscosity to glycerol is 2.5 to times that of the glycerol at 27.5 C.

At least partially deacetylated chitin as referred to above is readily soluble in a variety of acids to produce solutions of varying concentration of any order desired. Concentrations of from 0.5% to 50.0% and higher are readily produced. In accordance with the present invention for the shrinkproofing of wool such high concentrations will never be necessary and modest concentrations of the order of from about 1 /2 to 10% of the water soluble acid salt of the at least partially deacetylated chitin may be employed. For the production of such water soluble salts a wide variety of acids may be employed. One of the most readily available and easily employed is acetic acid which readily produces the corresponding acetate from deacetylated chitin which acetate is readily soluble in water or acetic acid, and the examples given below illustrate the use of acetic acid and formic acid for these purposes it being understood however that a wide variety of other acids may be employed. Among the acids which may be utilized in producing such derivatives are the monobasic aliphatic acids such as acetic, propionic, isobutyric and the like,

or their halogenated derivatives such as chloroacetic, alphabromo-normal butyric, dichloroacetic, various substituted acids containing ,alkyl groups, hydroxy groups, unsaturated groups, etc., such as trimethyl acetic, glycollic, lactic, hydraacrylic, hydroxy isobutyric, acrylic, ethacrylic, crotonic, levulinic, acetoacetic, pyruvic, and the like; and even salts of higher acids such as the fatty acids and even unsaturated acids from glyceride fats and oils may be employed in this group including such acids as lauric, palmitic, stearic, linoleic, and the like; polybasic acids may be employed including both aliphatic and aromatic polybasic acids such as succinic, malonic, phthalic, azelaic, sebacic, oxalic, malic, tartaric, citric, maleic, fumaric, diglycollic, dilactylic, and the like; acids containing aromatic nuclei, such as benzoic, benzensulphonic, sulfanilic, cinnamic, benzoyl benzoic, phenylacetic, and the like, and other miscellaneous acids including naphthenic, furyl acrylic, thioglycollic, cyanuric, hippuric acids and the like. Inorganic acids also maybe used to produce salts; such inorganic acids including hydrochloric, phosphoric, sulphuric, hydrobromic, boric, sulphurous, and polybasic acids as well as their acidic salts may be employed such as sodium bisulfite, sodium bisulphate, sodium dihydrogen phosphate, and the like. While a variety of acids are thus available for the production of salts, in the treatment of wool it is desirable to use mild acids in the production of the salt from the deacetylated chitin for impregnation of the wool or woolen fabric. The lower fatty acids serve very well for-"this purpose and will be used to. illustrate the variety of acids available in the particular examples given below.

The amount of the water soluble salt of the at least partially deacetylated chitin which is deposited on. the Wool must be controlled so that it is suflicient to give shrinkproofing without interfering with the normal hand of the wool. Ordinarily the amount of salt deposited on the wool and therefore of the amount of diacetylated chitin ultimately obtained therefrom, will correspond with about 1 /2 to 10% of the at least partially deacetylated acetate or its equivalent when other acidsare: employed. A deposit equivalent to from 2.0 to 5% of the deacetylated chitin acetate is, preferred for present purposes and will usually be sufficient for any shrinkproofing operation desired. The wool may be impregnated with the desired aqueous solution of the acid salt of the at least partially deacetylated chitin of the character set forth above, by a padding operation, and excessliquor then removed. Desirably the impregnated wool is dried at a relatively low temperature as for example a temperature up to about 70 or and preferably around 60 C. After the drying operation when such is used, the impregnated wool or woolen fabric may be baked at .a relatively high temperature in order to secure the shrinkproofing effect. The temperature employed is dependent on the time utilized in such baking operations. Ordinarily the temperature employed will be above C. in order not to lengthen out the baking time which is required, to excessive periods which interfere with commercial operation. Desirable shrinkproofing is secured when a baking temperature for example of C. for a time of 5 to 20 minutes, particularly 1'5 minutes, is employed. Any temperatures may be employed so long as they do not interfere with the wool or the desired chitin derivative deposit thereon. Excellent results are obtained'by such heat treatment in the immediate vicinity of 130 C. for the time given in that the shrinkproofing effect remains despite working. 'It must be remembered that during the baking operation, the. salt of the at least partially deacetylated chitin undergoes change, a good part or which, if not all of such change when baked or heated in an open vessel, being loss of the salt forming acid with the formation of deacetylated chitin in a water insoluble form. Thus, the use of non-degraded chitin tends to give baths which are relatively non-viscous at a given concentration of, say, 2.5% chitin salt. Wool treated with such solutions, dried and baked will exhibit shrinkproofing.

Various additives may be added to obtain special efiects such as enhanced softness and flexibility and in some cases, the shrinkproofing effect may be increased. It has been found, that improved effects maybe secured by incorporation of from 1 to 4% of a polyhydric alcohol such as glycerol, sorbitol, mannitol, and higher molecular weight polyglycols such as carbowax 1500 and 4000. Such additives as carbowax 4000 have been found to partially plasticize the baked chitin coating and prevent it from fiaking'ofl. In addition, ethers particularly polyhydi'o'x'y lated may be modified by reacting it with either an aliphatic or an aromatic halide to form modified chitins which tend to deposit a more flexible, wear-resistant film 0n the wool. It has also been found that allyl chitin prepared for example, by

steeping deacetylated chitin in 50% is particularly useful because it exhibits such advantages as lower viscosity for higher concentration of solids;

faster cure at lower temperatures; softer feel to the wool and internal plasticization of the chitin.

The reaction between a deacetylated anhydrochitosamine residue of the chitin (Ct-H1104N) and the allyl halide probably results in (1) Alkylation of the free amine group and/or (2) Etherification of the free hydroxy groups Additional and special effects are obtained with some of these derivatives, for example the addition of allyl sucrose gives a chitin coating that is more flexible and more resistant to abrasion. While a lyl chitin has been employed as a typical example of this phase of the invention, numerous other chitin derivatives of this particular type are applicable, i. e., those in which groups of longer chain length than allyl are used. Thus in place of allyl halide, any unsaturated aliphatic halide may be used, preferably containing more than two carbon atoms, since vinyl type halides are not generally very satisfactory. C'rotyl, methallyl, etc., halides such as the bromide, etc., may be used.

While the present application has described in detail the setting of the chitin on the wool by heat, it is to be understood that such a setting operation may be secured by the use of a setting or precipitating agent. For this purpose the wool may be first impregnated with the desired partially deacetylated chitin bath (with or without the heretofore ment oned additives) and the V excess liquid removed. The impregnated wool may be dried as heretofore described or passed directly while wet into the bath containing the setting agent, rinsed, and dried. If desired it may then be baked as heretofore described although this is not necessary. A wide variety of setting agents may be employed but should be carefully chosen to be certain that there is no undesirable or deleterious effoot on the wool or the chitin derivative. The setting or precipitating agents generally divide themselves into two groups. One group includes the organic precipitants particularly in the nature of surface active agents, more particularly of the anionic type. There are such a variety of surface active agents of this type available, that no attempt will be made to mention all .of them ,althougha number of groups and illustrative particular. materials are herein given. They may be of the carboxy acid type, or sulphuric esters including sulphated esters and acids, sulphated amines, sulphated alcohols, sulphated olefins, sulphonated oil type, alkane sulphonates, including petroleum sulphonates, alkyl aromatic sulphonates, including for example, alkyl naphthalene sulphonates, etc., and various other types particularly of anionic hydrophilic group containing agents. Generally, they may be said to fall into the groups of sulphates, sulphonates, phosphates, phosphinates, phosphonates and phthalates. Thus alkyl aryl sodium sulphonates, alkyl sodium sulphates, polyphosphates, etc., may all be desirably employed. These surface active agents are employed in the form of water soluble salts generally the salts of alkali metals or of ammonia, frequently magnesium salts may be employed and also quite often the alkaline earth metal salts but the salt employed should be soluble in water to the extent desired that an aqueous solution may be employed as the setting agent.

The following examples given below are illustrative and should not be considered to be limiting as to the scope and teachings of the present application.

Ewample 1 A padding solution containing 2.5% solids was prepared by dissolving 2.5 parts of deacetylated chitin, in 97.5 parts of a solution of 2.5 parts of glacial acetic acid in 95.0 parts of water.

A 25% solution of this chitin in 25% aqueous acetic acid had a viscosity of 13.1 centipoises at 25 C.

Squares of wool flannel were immersed in the treating bath until completely wet, the excess liquor removed by passing the fabric through squeeze rollers, and the samples dried at 60 C. From the amount of liquor picked up by the padding operation and taking the solids percentage of the liquor into consideration, the amount of solids deposited on the wool was calculated. After drying, the swatches were curved at different temperatures for various lengths of time. The curing conditions and the amount of solids deposited on the wool (in percent based on the weight of the wool) are tabulated as follows:

Percent of solidsfe- .835525 P Curing pos1 e on inie, min.

W001 ture, O.

Before treatment, four lengths of 8 each were marked on each of the samples including an untreated control, two in the direction of the warp and two in the direction of the fill. From these measurements the area in square centimeters was calculated. All the samples, with the exception of the untreated control piece (No. 5) were then treated as outlined above, dried without tension and cured. All the samples including the control were given a standard relaxation treatment (consisting of immersing the pieces in a 1% neutral soap solution at room temperature and allowing them to remain in this solution for 2 hrs. without agitation), rinsed and dried. The samples were then remeasured and the relaxation shrinkmachine, rinsed, dried, conditioned by allowing them to remain flat and without tension for 24 hours and remeasured. From these measurements the total shrinkage was calculated, which, minus the relaxation shrinkage, gave the value for the actual washing shrinkage.

The washing shrinkage for the above samples .is given in the following table:

+ denotes percent gain in area.

Example 2 A padding bath was prepared by dissolving 2.5 parts of deacetylated chitin (having a viscosity equal to that of the deacetylated chitin used in the previous example) in a solution consisting of 2.5 parts of 100% formic acid in 95 parts of water.

The treatment and the method for determining the washing shrinkage was similar to that described in Example 1.

The curing conditions, pick-up and percent Three swatches of wool were padded from a solution containing 2.5% deacetylated chitin (having the same viscosity as the chitin used in Example 1), 2.5% acetic acid and 95% water.

The amount of solids deposited on the 'wool was calculated from the weight increase resulting from the padding operation. Afterwards the padding swatches were dried and cured.

The curing time and temperature and the amount of solids expressed in percent of the orginal weight of the wool sample are given in the following table:

Percent of Curing soliitisdde- Tetm- 9 p051 e on era ure,

wool p O 0.

The treated wool including an untreated swatch was then measured, relaxed and washed as described in Example 1.

The following results were obtained;

Percent. Relative Viscosity Pick-Up,

(at 2w 0.) Percent 33% 2.4 0.0 2. 5 0.0 2.2 0.0 4.38 2.4 0. 5 4 Control (untroated) 2i. 1

Example 5 Padding liquors were prepared by dissolving deacetylated chitin of varying relative viscosity, in dilute acetic acid. In each case the padding solution contained 2.5% deacetylated chitin, 2.5% acetic acid and water.

The method of treatment and the determination of the washing shrinkage was carried out as outlined in Example 1. Each treated swatch was cured for 15 min. at C.

The viscosity of the deacetylated chitin, as expressed in centipoises for a 25% solution in dilute acetic acid (containing 25% CHaCOOI-I) at 25 C., the pick-up and washing shrinkage are tabulated below:

Percent Pick-Up, Viscosity (cps) Percent Shares ge 3.2 3.7 3. 1 4. 9 3. 2 3. 7 8.6 3. 4 4. 6 5 untreated control. 35. 0

Example 6 Padding liquors were prepared by dissolving deacetylated chitin in acetic acid and water as follows: (1) 2.5 parts of deacetylated chitin 2.5 parts of glacial acetic acid 95.0 parts of water 2.0 parts of deacetylated chitin 2.0 parts of glacial acetic acid 96.0 parts of water 1.5 parts of deacetylated chitin 1.5 parts of glacial acetic acid 97.0 parts of water.

Three swatches of wool and a control piece (No. 4) were then treated as outlined above, dried without tension, baked at 130 C. for 15 minutes and given the standard relaxation and washin treatment described in Example 1.

The washing shrinkage and percent pick-up :for each of the above samples is given in theiollowing table:

Pircent rea Pe eut Shrinkage No. 55; As es (Washing) 70 p Shrinkage L 5.5 1 3.2 8 9 4.1] 2 2.3 &8 "l- 6.0 '3 1.7 1.5 Ilmtl'flfl 33. 0 Z18 Example 7 50 parts of deacetylated chitin, 50 parts of acetic acid, and 1900 parts of water were mixed together to give a solution having 2.5% chitin 5 in 95 parts of water was prepared. One swatch gfiz gg gg gggiig 3 :28; of wool was treated and baked for 15 minutes at Solution there was added 130 C. The treated swatch and also a control were then treated as described in Example 1.

(1) no additive The shrinkage and pick-up is shown in the table. (2) 10 parts of 96% glycerol 10 (3) 10 parts of Arlex 1 and hexamethylene Percent tetramine in the ratio of 80% Arlex and 55.23% A 20% hexamethylene tetramine Shrmkage (4) 10 parts of polyethylene glycol 1 3 2 5 (5) P s Of 1500 dfiilidfiiir'fdjIIIIIIIIIIIIIIIIIII 3515- (6) 10 parts of carbowax 4000 (7) 10 parts of allyl sucrose containing 0.1%

cobalt acetate.

Arlex" is an aqueous solution of sorbitol. Carbowax is a high molecular weight polyethylene glycol.

Three swatches each and a control piece (No. 8) were then treated as outlined above in Example 1, dried, and baked at 130 C. for 15 minutes. Swatch A was relaxed and washed follow- 10 dried at room temperature under a vacuum of 20 mm. 20.2 parts of a soluble modified chitin was secured. A padding bath containing 2.5

parts of the above chitin, 2.5 parts of acetic acid Example 9 10 parts of deacetylated chitin, 10 parts of acetic acid, and 380 parts of water were mixed together to form a clear padding bath containing 2.5% solids. Three swatches of wool were immersed in the padding bath for 5 minutes; the excess liquor was removed by passing the fabric through squeeze rollers. The padded swatches ing the standard procedure. Swatch B was hand t worked for 15 minutes and relaxed and washed. gs igz gg si fg gl g for 1 hour Swatch C was relaxed, hand worked for 15 min- 2 was dried at 0' C for 1 hour and then utes and washed. The following table gives the baked for 15 minutes at 0 Q percent pick'fups t percent area Shrinkfege for No. 3 was immersed in a bath of 2% aqueous each sample including the control. The pick-ups Sodium dodecyl toluene sulphonate, rinsed and in each case are determined as deacetylated dried for 1 hour at 600 chmn plus addltlve- The washing shrinkages and percent chitin Percent Percent pick-ups are as follows: No. Pick-up area (Total) Shrinkage No Pew? Chitin Pekrrcegit I Eek-Ups Shrinkage 18.2 2 0.6 3.5 4.1 4 control (untreated) 26.9

Control Example 8 178 parts of deacetylated chitin was steeped in 400 grams of a 50% aqueous solution of sodium hydroxide for 6 hours at 20 C. The excess alkali solution was removed and the wetted chitin placed in a 500 ml. three-neck flask provided with a thermometer, water-cooled condenser, and mechanical stirrer. 12.1 parts of allyl bromide and 250 parts of benzene were added and the reaction mixture heated at 70-80 C. with rapid stirring for 3 hrs. The modified chitin was washed free of alkali and benzene and rapidly Example 10 Seven swatches of wool were treated with a solution of deacetylated chitin similar to that used in Example 1. After the wool square had been thoroughly impregnated, the excess liquor was removed by passing the fabric through squeeze rollers. From the amount of liquor picked up by the padding operation and by taking the concentration of the liquor in consideration the amount of solids deposited on the wool was calculated. After padding, but before drying, the samples were immersed in setting baths prepared by dissolving 5 parts of the various setting agents in 250 parts of water for approximately 15 min. The samples were then rinsed and dried.

The area shrinkage on washing was determined by the method outlined in Example 1.

The composition of the setting baths, the percentage of solids deposited on the wool and the percentage of area shrinkage on washing are tabulated below:

Percent Percent Solids No. Deposited on W001 Setting Agent Trade Name shgxriaage 1 3.0 Na5(capryl)s(PaO1o)z "View-Wet 58B 6. 0 2-. 3.0 Na alkylnaphthtalene sulionate Nekal BX 2.0 3 2.9 Na lauryl sulfate Duponal ME dry. 5. 9 4 3.1. C -Ha3CON(CHa) C H4SOaNa Igepon T" 15. 1 5 3.2 Dloctyl sodium sulfosuccmatc "Aerosol OT 4. 8 6.. 3.2 Na dodecyl toluene sulfonata. 0

7 3.3 a amido alcohol sulphate sulframide DT 8.4 8 untreated controL. 35. 9

Example 11 The wet specimens were then immersed and Four swatches of wool were treated with the ggggg for 15 mmutes m the followmg Settmg 2.5% deacetylated chitin solution of Example 1.

The amount of deacetylated chitin deposited on 1. 5 parts dogecyl benzene phos- Neutralized gin: l 3. ueous O um the wool was determined from the liquid pick-up. 2. 5 g g g acid hgdroxidg and The swatches were immersed in aqueous setting 5 parts d-sulfohphthalllitilai liydrilde resuit g s baths of various compositions for approximately 5 5% tetra: t a

e with water to min. followed by rinsing and drying at 60 C. 44' diamino stilbene 22' disula total of 250 The area shrinkage on Washing was determined 10 6. 5 i t 221 311onium-2-nitrobutane-l-sul i af e dissolved by the method outlined in Example 1. in 2 5 parts of water .5 rt d in dd idin rts The composition of the setting baths, the solids gi so mm 81 e 1850 V8 3 pa deposited on the wool, expressed in percent based 10 parts sodium zirconyl sulfate dissolved in 250 parts water on the weight of the wool, and the percentage of 15 10 parts sodium metasilicate dissolved in 250 parts water area Shrmkage on Washmg were as follows- 10. parts sodium tungstate dissolved in 250 parts water 4 Cone. of Percent Percent Solids De- No. posited on the W001 Setting Agent Trade Name sgrlgsttlg, shgggge 1 3.0 Na dodecyl toluene sulionata. 2 0

anhydrous sodium sulionata. 15 1,0 3 2.8 sodium alkyl aryl sulfonataacconal NR" 2 0 4 untreated controL- 27.2

Example 12 Eleven swatches of wool were immersed in a padding solution containing 2.5% deacetylated chitin, 2.5% glacial acetic acid and 95% water. After the pad liquor had thoroughly penetrated the fabric, the excess liquor was removed by passing the material through squeeze rollers, thereby removing the excess pad liquor. A 25% solution of the deacetylated chitin used in this experiment in 25% aqueous acetic acid had a viscosity of 6.6 centipoises at 25 C. The swatches were then placed in setting baths of various composition, without previous dryings except in the case of sample No. 6 which was dried before being brought in contact with the setting bath. After having remained in contact with the setting bath for about 10 min., the samples were rinsed and dried at C.

Area washing shrinkage figures were obtained by the procedure outlined in Example 1.

The amount of deacetylated chitin deposited on the wool, calculated from the amount of liquid picked up by the padding operation, the composition of the aqueous setting baths and the area shrinkage are tabulated below:

The samples were then thoroughly rinsed and 2 dried at 60 C.

cording to the procedures outlined in Example 1. The amount of solids deposited on the wool was calculated from the liquid pick-up which resulted from the padding operation.

The area shrinkage and percentage of solids deposited based on the wool weight are listed below:

Percent Solids i s Deposited on Swatcl Shrinkage Percent Percent No. Setting Agent Trade Names Cone" sohds Area percent dep on wool Shrinkage 1 Tetrasodium pyrophosphate 5 3. 1 7. 5 2. Na dodecyl toluene sulfoneta- 2 3. l 1.0 3 Na5(capryl)5(PaO1o)a 2. 8 3.1 1.0 4 Na (2 ethy1hexyl) (PsOro)2. 2. 8 3. 2 1. 9 5 anhydrous sodium sulfate 15 3.0 6.9 6 -do l5 3. 1 0 7. Na hydrocarbon sulfonate.- 2 3. 3 3. 5 8..- Na arylalkyl polyether sulfate..- 8 3. 2 3. 0 9 Na petroleum sulfonates. 2 3. 3 7. 4 10 Na aryl alcohol sulphonate Santol S" 2 3. 3 6. 7 l1 Na fatty alcohol sulphonate Sandopon P0- 2 3. 5 1. 5 12. Untreated control 34. 3

Example 13 Example 14 A series of flannel squares were immersed in A square of wool flannel was immersed in each a solution made up from 25 parts of deacetylated of the following pad liquors:

chitin, 25 parts of glacial acetic acid and 950 L 5 parts of deacetylated chitin dissolved in a parts of water.

solution containing 7.6 parts of lactic acid and A 25% solution of this deacetylated chitin in 7 181 4 parts water.

zii i g i gi 222 g acid had Vlscoslty of 2. 5 parts of deacetylated chitin dissolved in a mixture of 8 parts conc. hydrochloric acid When the swatches had completely wet out, 37.8% and 187 parts Waten they were removed from the pad liquor and the excess was removed by passing them through The excess pad liquor was removed by passing squeeze rollers. the samples through squeeze rollers, and im- The washing shrinkage was determined acsodium salt of dodecyl toluene sulfonate for about 15 min. The samples were then rinsed and dried.

The amount of solids deposited on the wool calculated from the liquid pick-up resulting from the padding and the area shrinkage on washing determined according to the procedure outlined in Example 1, are listed below:

Percent SolidsdDefff f posite on the Wool shrmkage Example 15 A series of padding baths was prepared having the following compositions:

The viscosity of bath when diluted with an equal weight of water amounted to 13.1 centipoises at 25 C.

Weighed squares of wool flannel were immersed in the above padding baths until completely wet out, the excess liquor was removed by passing through squeeze rollers and swatches were reweighed. Taking the concentration of the pad liquor in consideration, the amount of deacetylated chitin deposited on the wool was calculated from the weight increase.

The wet specimens were then immersed in a solution containing sodium tungstate (Na2WO4.2H2O) and worked around for about min., rinsed and dried at 60 C.

The amount of solids deposited on the wool and the amount of shrinkage when the samples were washed according to the procedure outlined in Example 1 are listed below:

ment was followed by drying at 60 Example 16 I A padding solution was prepared by dissolving 10 parts of deacetylated chitin in a solution of 10 parts glacial acetic acid in 380 parts of water.

A solution containing .25% of the deacetylated chitin, .25% of glacial acetic acid and 99.5% of water had a viscosity of 13.1 centipoises at 25 C.

Two swatches of wool were immersed in the pad liquor until thoroughly wet out. The excess liquor was removed by passing the fabric through squeeze rollers. The swatches were then dried at 60 C., whereupon one of them was passed through a setting bath containing 2.5 potassium cyanate and the other one was immersed in the same setting bath for 20 minutes with agitation. In both instances the potassium cyanate treat- C., rinsing and re-drying.

The amount of deacetylated chitin deposited on the wool calculated from the weight increase due to the padding and the washing were as follows:

- Percent Percent solids de- Area posited on the wool Shrinkage 2.9 11. 3 2.9 8. 3 Untreated control 37. 0

The following example will illustrate the use of setting baths of various types to give durable shrinkage control wherein flaking off of the chitin derivative has been eliminated. While as in previous examples, the chitin treated material was immersed in the setting bath before drying, the example given below illustrates a process where the wool, after padding with the chitin solution, is dried at 60 C. before the treatment with the setting bath. This latter procedure is believed to be preferable.

Example 17 40 parts of deacetylated chitin, 40 parts of acetic acid, and 1518.4 parts of water were mixed area shrinkage on Percent together to form a clear padding bath contain- Percent Solids Depositedonthewool area mg 2.5% chitin soh s. Several samples of meas shmkage ured wool swatches were padded with the above solution and, after removing the excess liquor 3:8 by passing through squeeze rollers, the swatches were dried at C. Three of these chitin- ?;3 treated swatches were then placed in aqueous solution of each of the following setting agents for a period of 15 minutes.

Ooncen- Bath No. tration, Setting Agent Trade Name Percent 2 Sodium dodecyl toluene sulfonate Pactivex" 2 Sodium alkylnaphthalene sulfonate Nekal Bx 15 Sodium sulfate 2 Sodium alkyl arylsulionate NaceonaI-NR 2 Na5(eapryl)5(PaOm)z victawetssB. 2 Sodium fatty alcohol sulfonate... Sandopan PO." 2 Sodium tungstate 2 Sodium aryl alkyl polyether sulfate Triton 720." 2 Cationic amide salt of a fatty acid ami Sftol AD. 2 Sorbitan monostearate polyoxyalkylene derivative. Tween 60. 2 Cetyl dlmethyl benzyl ammonium chloride 15 The three swatches from each bath were then dried at 60 C. Swatch A was relaxed and washed following the standard procedure. Swatch B was hand worked for 15 minutes and relaxed and washed. Swatch C was relaxed, hand worked for 15 minutes and washed.

The following table gives the percent pick-up:

and percent area shrinkage for each sample including the control. Also included are results obtained with samples which were padded with the deacetylated chitin solution, dried and baked at 130 C. for 15 minutes.

Relaxed and washed Handm rked for Hand-worked for 15 with no handmin. before rclaxmin. after relaxwashin'g ation ation $313 m 1 .333}. g 1 333.. g

(deacety- 33 (deacetyg; (deacety- 353 late lated a e lated we chitin) be ehitin') 3 chitin) s 3.3 2L1 3.4 3.7 3.4 3.2 3. 4 1.8-1 3.5 9. 4 3. 4 4.1 3. 4 2.0 3.5 6. 8 3. 5 3. 0 3.5 3.0 3.5 8.2 3.5 4.4 3.5 as 3.5 a 2.7 3.5 4.5 3.5 0.5 3.6 1.3 3.5 0.0 3.5 3.9 3.6 7.7 3.5 9.0 3.5 2.5 3.6 2.2 3.5 3.9 3. 6 12. 6 3. 6 12. 3 3. 6 12.9 3.6 11.1 3.6 11.8 3.6 11.4 3. 6 12. 1 3.6" 15. 2 3.6 14. 1 3.6 0.3 3.6 1.1 3.6 0.0 0.0 25.1 0.0 23.6 0.0 23.9

The anionic type wetting agents give the best results with sulfonated or sulfated products being generally most efiective. The cationic or nonionic types are not nearly as effective as setting agents.

Having thus set forth my invention, I claim:

1. The method of shrink-proofing unfelted Wool while retaining substantially normal hand which comprises padding the wool with an aqueoussolu-- tion of an acid salt of a substantially'undegraded at least partially deacetylated chitin to deposit from about 1.5 to 10% by weight on the wool, and baking the treated wool at a high temperature but below about 140 C. to avoid substantial injury to wool or the chitin derivative desired, to produce shrinkproofed wool retaining its substantially normal hand.

2. The method as set forth in claim 1 in which the salt is deposited in amount of from 2.0 to 5% and the baking is carried out at 'a tempera ture of from 110 to 140 C.

3. The method as in claim 2 in which the acid salt is a salt of a lower fatty acid.

4. The method of shrinkproofing wool while retaining substantially normal hand which com-- prises impregnating the wool by padding it with an aqueous solution of a salt of an acid with a substantially undegraded at least partially deacetylated chitin to deposit on said wool an amount of said salt from about 1.5 to 10% by weight on the wool to yield an amount of deacetylated chitin derivative sufficient to shrinkproof the wool while retaining substantially normal hand, removing any excess solution, and" setting said deposit on the wool by treating with an aqueous solution of a water soluble salt precipitating agent at a temperature between room temperature and about 80 C., the temperature used being one that does not insolubilize the chitin derivative by heat before being set by the setting agent, the salt being sufiiciently soluble to act as a setting agent, and the cation of the salt being selected from the group consisting step of drying after the deacetylated chitin has been set by the action of the setting agent.

8. The method as in claim 1 in which the nitrogen present as free amino groups in the chitin derivative is from '70 to 9. The method as in claim 1 in which the viscosity of the chitin derivative relative to glycerol is 2.5 to 50 times that of glycerol at 275 C.

10. Wool of substantially normal hand prooied by a heat cured deposit of substantially undegraded at least partially deacetylated-chitin in amount from about 1.5 to 10% by weight on the wool to give shrinkproofing without substantial change in hand. v

11. Wool of substantially normal hand carry ing a set substantially undegraded at least partially deacetylated chitin salt, the deposit being in amount from about 1.5 to 10% by weight on the wool to give shrinkproofing without substantial change of hand.

12. The method as set forth in claim 4 which includes the further step of baking the treated wool at a high temperature but below about C. to avoid substantial injury to wool or the chitin derivative desired to produce shrinkproofed wool retaining its substantially normal hand.

13. The methodas in claim 4 in which the v-iscosity of the deacetylated chitin is from 5 to 20 centipoises measured in a .25% solution of the deacetylated chitin in 25% acetic acid at 25 C.

14. The method in claim 4 in which the chitin is modified by reaction with a component selected from an aliphatic and an aromatic halide to give achitin containing an organic group derived from said halide attached to the nucleus of the chitin derivative.

15. The wool as set forth in claim 10 in which the chitin derivative has a viscosity relative to that of glycerol of 2.5 to 15.

16. Wool as set forth in claim 10 in which the chitin is modified by a component selected from an aliphatic and an aromatic group attached to the nucleus or the chitin derivative.

shrink-- 17 18 17. Wool as set forth in claim 10 in which the References Cited in the file of this patent deposit includes a minor amount of a component UNITED STATES PATENTS selected from the group conslstmg of polyalcohols and their ethers. Number Name Date 18. Wool as in claim 10 in Which the deposit 5 2,047,217 McQueen a1 July 1936 includes a, minor amount of an allyl ether. 2,173,243 Young sept- 1939 JOHN B. RUST. 

4. THE METHOD OF SHRINKPROOFING WOOL WHILE RETAINING SUBSTANTIALLY NORMAL HAND WHICH COMPRISES IMPREGNATING THE WOOL BY PADDING IT WITH AN AQUEOUS SOLUTION OF A SALT OF AN ACID WITH A SUBSTANTIALLY UNDEGRATED AT LEAST PARTIALLY DEACETYLATED CHITIN TO DEPOSIT ON SAID WOOL AN AMOUNT OF SAID SALT FROM ABOUT 1.5 TO 10% BY WEIGHT ON THE WOOL TO YIELD AN AMOUNT OF DEACETYLATED CHITIN DERIVATIVE SUFFICIENT TO SHRINKPROOF THE WOOL WHILE RETAINING SUBSTANTIALLY NORMAL HAND, REMOVING ANY EXCESS SOLUTION, AND SETTING SAID DEPOSIT ON THE WOOL BY TREATING WITH AN AQUEOUS SOLUTION OF A WATER SOLUBLE SALT PRECIPITATING AGENT AT A TEMPERATURE BETWEEN ROOM TEMPERATURE AND ABOUT 80* C., THE TEMPERATURE USED BEING ONE THAT DOES NOT UNSOLUBILIZE THE CHITIN DERIVATIVE BY HEAT BEFORE BEING SET BY THE SETTING AGENT, THE SALT BEING SUFFICIENTLY SOLUBLE TO ACT AS A SETTING AGENT, AND THE CATION OF THE SALT BEING SELECTED FROM THE GROUP CONSISTING OF THE ALKALI METAL, AMMONIUM, THE ALKALINE EARTH METALS, AND MAGNESIUM. 